Process of making polyhydroxy carbon compounds



Patented Apr. 2 6 192 7.

maize Essex, or 'svnacusn, iimw YORK, hm)

. ,rrmusznvama, assrpnoaswon. 1. no PON'I.

imm ron DE WAKE.

rnocfifss or'iloiiinnaokrcannbii continuing m, "Drawing; ta t spa This-invention relates to theproduction of polyhydroxy compounds troin organic come pounds"contain'ing at least one pair ofcarbon atoms united by'f'fa "double bond.-*-;I'n general our 'inv'ention' compr ses converting an undri'n, in such a way that the resulting reac-.

tion mixturecontains water and an alkali forIIii-ng' metal carbonate such as sodium or 10 calciunrcarbonatein addition to saidhalo- I hydrin; and then heating said reaction mixture to bring about hydrolysis of thehal'ohydrin; One particular embodiment of the invention is inthe production ofglycerin division of our application erial No. 340,- OT B'fiI'ed'in the United States Patent Oliice November 2 2, 1919, Patent Number 1,594,608, granted August 3. 1926. In an investigation to find processes most suitable for the 'conm'iercial synthesis "of glycerol we discovered that allyl chloride couldbe converted. with good yields, into glycerol dichlorh'ydrins by slowly passin'g carbon dioxide'into a mixture of allylchloride and "a water solution of an alkali, or

alkaline eartln'inetal hypochlorite, the resulting reaction mixture was so constitu'ted that conversion of the dichlorhy-j drins into glycerol could be readily effected simply by] heating the mixture, preferably with the addition of a further-quantity of carbonate. This. process is described and claimed in our Patent No. 1,477,113 dated December 11, 1923.

We have now found that compounds containing an ethylenic linkage may be converted in an analo ous manner then by hydrolysis, and without isolation of the halohydrins, into the corresponding alpha-glycols. The compounds which may be caused to undergo the above described transformation vary '\'videly in molecular structure and in chemical and physical properties, but they are all characterized by possessing a pair of doubly linked carbon atoms so situated with respect to the rest of the molecule aS'to be capable of combining additively with the OHand Cl radicals of hypochlorous acid to form chlorhydrins. Examples of such compounds are (1) olefines,. -such as ethylene, propylene, butylene, etc.; (2) aryl-substioaroaa'nonon E AWARE;

f pucajaiia cleanings 192s. Serial saturated organic compound into ahaloh'yfrom allyl' alcohol. This" a plication is aand that.

other carbon first into the corresponding halo hydrins, and

DE NEMOURS? OFI'WI IE olli'fl'ld weath 2 "1 9, "s'eri l 840.073. jfn v'iidedmfa am no. 111,6s5.-: p tute'd alkylenes,'s'u h as styrole' (phenyl'e'thylone or vinylbenzene); and?) substituted 6 olefines with miscellaneous sustituents,si ich 2111s 1)gaminaliydroitypropylene j (allyl'j' 1m. Our new processinay be iIIustratedbyjthefollowing examples: Q A

, I (Ethylene 9131601.-

To prepare ethylene glycol according to this method lSQ cu. ft.- ofv ethylene and 241 cu. ft. of carbondioxide, measured at stanolard conditions, are passed into a .cold"5}.'i hypochlorite solution containing 1001103; of sodium hypochlorite The ethylene" should preferably be admitted to the solution in the formof very fine bubbles, which may be ac-. 7 complished by forcing the ethylene through the pores'of unglazed earthenware. The so? lution should be kept .coldthroughout the; operation and thecarbon dioxide admittedsufficiently slowly to keep tion of free hypoc'hlorous acid.' The resulting solution of ethylene chlorhydrin is then heated to boiling under a reflux'condens er and keptat this temperature for several hours. If a test shows that chlorates are absent, the ethylene glycol formed maybe recovered by concentration and distillation.

The reactions involved are: m eeg+2 e +o z+ z 2(11'1 OH.CH OH+2NaCl-\GO I1 Phenyl glycol. 104 lbs. of styrole are added to 74.5 lbs. of 00 sodium hypochlorite in water solution, the mixtui'e vigorously stirred and carbon dioxide passed in, while keeping the mixture cool, until substantially all the hypochlorite has been decomposed. The chlorhydrin is then hydrolyzed to phenyl glycol by boiling the product under a reflux condenser. The reactions involved are:

low the ,concentra- 75 v a A 1,826,898

lbs. of sodium hypochlorite in water solualkali-forming metal carbonate to form :1. tion, the mixture vigorously stirred and carhalohydrin, and heating the reaction mix- 45 bon. dioxide assed into the cooled solution ture containing an alkali-formin metal caruntil, hypochlbrites have disappeared. The bonate to hydrolyze the halohy rin. a lycerine monochlorhydrin roduced is hy- 2. The process of. producing? a polyhygrolyzed to glycerine by boi ing the product droxy carbon compound whic 1 comprises under a reflux condenser. The principal retreating a mixture of a substituted olefine, 5o actions involved are: having an, oxygen-containing substituent,

2CH OHCH CH-+2NaOC1+CO +H 0 and a water solution of an alkali-forming 2 2 a 2 metal hypochlorite' while keeping the mix- OH'CHCLCH2OH'+N%CO3' turecool, with caibon dioxide to convert.

H 0H CHOH OH OH+2NaGl+CO said hypochlorite into an alkali-forming metal carbonate and into hypochlorous acid As evidence of the wide applicability of under such conditions that said acid 'com-,

this process there may be mentioned the pro-' bincs almost immediately with the substiduction, in a manner similar to that clvetuted olefine to form the corresponding scribed in the receding examples, of chlorhydrin, and then heating the resulting phenylglyceric acid mixture to bring about 'a reaction between the water the alkali-formin metal car- (GHE'CHOH'QHOH'COOH) 1 bonate, and the chlorhydrin, aiid tothe i'eby from cinnamic acid tram}1 a3 alkali-forming metal halide and v t"v t'tt (OHrCH:CH.O-OOH), oplrgfyngr roxy (cuva ne of sad an )s 1 u er of dih droxystearic acid from oleic acid, 3. The process 01' producing glycerin and of trihydroxyste'aric acid from riciwhich comprises causing all 1 alcohol to n'oleicacid. combine with hypohalous acid in the pres 1 Various changes may be made in the procence of an, alkali-forming metal carbonate ,ess set forth in detail above Without deto form a ci'ilorhydrin, and'heating the reparting from our invention. Thus in place action mixture containing an alkali-formof the alkali-forming metal hypoehlorite re-. ing metal carbonate to hydrolyze the chlorferred to above, there may be used other hydrin. v hypohalites' such as sodium, calcium, or 4. The process of producing glycerin barium hypobromite; the resulting halohywhich comprises passing carbon dioxide in drins are then hydrolyzed to dihydroxy comto a mixture of an aqueous sodium hypopounds by heating the reaction mixture as chlorite solution and allyl alcohol, while described in the specific examples. keeping the mixture cool, to form sodium e claim carbonate and a chlorhydrin, and then beat 30 1. The recess of producing a polyhying the mixture until the chlorhydrin is droxy car on compound which comprises hydrolyzed to gylcerin.

causing a carbon compound containing a In testnnony whereof we ailix our signapair of doubly llnked carbon atoms and an tures. oxygen-containing substituent to combine HARRY ESSEX.

flwith hypohalous acid in the presence of an I ALGER L.- WARD. 

